Treating cellulose derivative materials



Patented Apr. 9, 1940 UNITED STATES 7 TREATING CELLULOSE DERIVATIVE MATE RIALS Joseph B. -Dickey, Rochester, N. Y., assignor' to Eastman Kodak Company, Rochester, N. Y., a

corporation of New Jersey No Drawing. Application December 17, 1938,

Serial No. 246,511

4 Claims. This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed of organic derivatives of cellulose such as cellulose 5 acetate, cellulose propionate, cellulose acetate propionate, and cellulose acetate butyrate, to render them more amenable to textile operations such as knitting and the like. This invention also relates to compositions of matter in which cellulose derivatives such as cellulose acetate, cellulose nitrate or cellulose ethers,

-- are combined or mixed with other substances,

such as a compatible plasticizenand a common solvent for both, with or without other useful addition agents, so that the resulting product will have properties such as will make the composition highly advantageous for use in the plastic and analogous arts, such for instance, as the manufacture of wrapping sheets, photographic film, artificial silk, varnishes or lacquers, and the like. T As is well known in the manufacture of yarns, particularly those composed of or containing cellulose Iorganic derivatives, it isnecessary to treat the yarn in order to reduce the tendency toward breakage of the individual filaments or fibers when they are subjected to various mechanical strains andto lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, and winding and reeling. It is also necessary to treat yarn to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In knitting, it is particularly important that the yarn be soft and pliable in order that it may confor m readily to the contour of the needles and thus provduce a closely knit fabric free from such defects as stitch distortion, pin holes, ladderlng, and the like. 4 Heretoiore it has been proposed to employ softening agents such as polyhydric alcohols and similar agents as ingredients of yarn conditioning 'or lubricating formulas, generally in connection with mineral, animal or vegetable oils. It 45 has been found, however; that most of the known softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is. high vapor pressure, and in some cases too drastic a solvent action 30 on the yarn. Many of such agents possess slight or insumcient solvent power for the lubricants with which they are used, and itis accordinglynecessary to employ blending agents or emulsifying agents in order to obtain operable yarn treat-- 5 ing formulas. In addition, many of the known softening and lubricating agents are. insumciently soluble in water. to' permit satisfactory removal by aqueous scour baths.

While in the plastic and related arts cellulose for decades, it has also been known that to utilize them it is necessary to mix therewith such plasti cizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose of reducing the infiammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness, and other properties which will enhance the value of the resulting product. Addition products for the same or similar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquersr varnishes, artificial silk filaments, moulded compounds and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives have been put and the increasing number of desirable properties required of the cellulose derivative for most purposes has made the discovery of new and economical plasticizers or other addition agents, a matter of considerable importance to the art.

This invention has as its principal object to moved .from the yarns by the usual scour baths.

'A still further object is to provide an improved method forthe conditioning of yarns, particularly those composed of or containing organic derivatives of cellulose such as, cellulose acetate, whereby the. yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object is to provide an improved type of yarn which is especially amenable to textile operations including circular knitting, weaving, spinning and the like. Still another objectof this invention is to produce a composition of matter which may be made into permanently transparent, strong and flexible sheets or films of desired thinness which are substantially waterproof, are unaffected by ordinary'photographic fluids and possess the desired properties of a. support for sensitive photographic coatings. Yet another object of 'my invention is A Still to produce a composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such as in the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, to produce a composition which will not injure, or be injured by, the substancesor surfaces with which it is associated during manufacture. hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that ketals selected from the group consisting of monoand di-ketals derived from acetonyl acetone and having the general formulae:

Other objects will appear where R and R are substituents selected from the group consisting of alkoxyalkyl, and heterocyclic groups, wherein free hydroxy groups may be reacted with suitable aliphatic, aromatic and heterocyclic acids, -acid chlorides and anhydrides, and where R and Ram in addition to R and R hydrogen, may be used as yarn conditioning agents and particularly as softening agents, with or without the addition of animal, mineral, or vegetable oils, in the treatment of yarns composed of or containing organic derivatives of cellulose. I have found that these compounds when employed as described in the detailed examples set forth below have a slight solvent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at. the same time having too drastic an action thereon.

The derivatives of this invention form a valuable series of solvents, softening and plasticizing agents for organic derivatives of cellulose including cellulose acetate. For example, these compounds may be included in cellulose acetate spinning dope and the threads thus prepared are very soft and pliable and of value for certain textile operations including knitting.

I have also found that these compounds are excellent solvents for organic derivatives-of cellulose including cellulose acetate and may be used alone or in conjunction with other materials in the production of films, lacquers, molded products, etc., composed of these materials.

My invention also comprises the discovery that valuable properties may be included in and/or contributed to compositions containing cellulose derivatives such as cellulose acetate, by adding thereto as plasticizing compounds the above mentioned compounds. This class of compounds is compatible with cellulose derivatives and particularly compatible with cellulose acetate in the percentages hereinafter given.

PREPARATION OF COMPOUNDS methods. Improved results are obtained in many cases if a catalyst, such as ferric chloride, sulfo salicylic or furoic acid, etc., be used.

Acetonyl acetone glycerol Ten moles acetonylacetone, eight moles glycerol, one liter benzene are heated in the presence of a trace of ferric chloride in such a manner that the water is continuously removed from the reaction. Heating is discontinued when eight moles of water have been collected. The mixture is then treated with a small amount of sodium carbonate, filtered, and distilled. The desired product has a B. P. 1'738/20 mm.

Diglycerol acetonylacetone Diacetate of diglyperol acetonylacetone One mole of diglyceryl acetonylacetone is treated with excess acetic anhydride (2.2 moles) under reflux for 2 hrs. The solution is then fractionated to give the ester, B. P. /90/1-2 mm. The propionate may be prepared similarly-B. P. 2536/20 mm.

TREATMENT or TEXTILE Yarms In accordance with the invention these compounds may be applied directly to the yarn during or after spinning, or'may be added to the spinning solution itself. I have found that these compounds have exceptional solvent powers which enable them to dissolve mineral oils and blown and unblown, drying and semi-drying, vegetable and animal oils and accordingly they may be, and preferably are, employed as ingredients of yarn conditioning or lubricating formulas in conjunction with agents which function wholly or partially as lubricants.

In the following examples and description I have set forth several of the preferred embodiments of my invention, but they are included merely for purposes of illustration and not as a limitation thereof.

My invention will be more readily understood by reference to the following examples in which typical applications of the invention are set forth.

Example 1 A compound having the formula CHaCCzHl-C 0-C1I3 (monoglycerol acetonyl acetone) is applied to textile materials (silk, wool, .viscose, cellulose,acetate, etc.) by means of a wick, roller, spray, bath, pad, etc., to facilitate their knitting, weaving, spinning and the like. If the yarn is intended primarily for knitting the amount ofconditioning liquid applied may vary from 4-25% by weight of the yarn, and if the yarn is intended for weaving, the amount of liquid applied may vary between 1-5% by weight of the yarn.

Example 2 Example 9 Parts Part8 CHr/C C:H&COCH: CHa-C-CHa-CHr-CO-CH: I

0 0 o CH -CH: 2o

CHz-cH-CHrOg- 2H5 80 5 (monoglycerol acetonyl acetone propionate) GHQ-.0 H CH CHT O C O C CH2 Olive oil 20 011,-0 H, 0 and applied to textile materials such as silk, wool, cellulose acetate, viscose, etc.,as described above. 0

If the yarn 1S linen (led primarily for knitting (Mono tetrol acetonyl acetone ditetraliydrofuroate) 10 the amount of conditioning l quid applied may g v g i g vary from 425% "by weight of the yarn, and if m for weaving, the amount of liquid applied may Example 10 yg g gzig? 3 g p i 2 f: A 20% solution of cellulose acetate in acetone c e amen S am t 8 as e in which is incorporated 1-25%, by weight of the l5 scribed are quite soft and pliable and give imcellulose acetate or proved results in various operations such as weav- J ing, knitting, etc. CHzCCHz-C 2C0GHa Other examples of yarn conditioning composi- O 0 2o tions which may be applied to various types of, C 2 C C 20gC 7H33 yarns, particularly those composed of or contain- (Monogyloeml acetonyl acetone 01 m mg cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and similar cellulose extruded through fine onfices mto an evapom organic acid esters in accordance with my inventwe atmosphere The filaments thus produced 5 tion and which render such yarns soft and pliable are Wound or twlsted and wound- Yams thus and especially well adapted for various textile produced operations, particularly knitting, are as follows: Examp 11 P arts Emmpze 3 Water 8O CH!. C,H4 Q CH. CHr-C-CHr-CHg-CO-CH 3o reg 10 a0 oHr-c11-c1 1loc-cH= Carroll-GENE (Monoglycerol acetonyl acetone acetate) 0 Water soluble cellulose ester 5 Sititititi 20 CH; CH-CHz-(OCgHM-OH 5 Example 4 0 CH3(JCH2 CHI/,-CCH3 Parts Emmple 12 0 O O 20 Blown neats-foot oil 70 CHg-CHCHz-OCOH3 cnron-cnl-og-cn, 40 (Diglycerol. acetonyl acetone dracetate) 20 Light mineral 011-. I l 80 (MCHTCHTCEIP? g g t o Any of the above compositions may be applied 0 Q ()H, 0H, to the yarn intended for use in circular knitting (mm-#331 by means of a bath wick spray roller pad or d l 1 I $853233??? bis fmethylene 30 any suitable means. The amount of conditioning Example 6 liquid applied may vary between 5-25% by weight 50 of the yarn. Usually however the amount of- OHCHOHz--H 3 C c c Parts conditioning liquid applied 1s about 10-15% by 00134-0033 Weight of the yarn. Yarn composed of cellulose 0 acetate conditioned as described above gives exgf gg g ggg a ggg cellent results when used in the circular knittin Neats-ioot oil process.

Example 7 As will be apparent from the above examples Parts and description the conditioning agents of my invention may be applied by a wide variety of 0cm methods. For example, I may employ the agent (30 g 8 as an ingredient of the spinning dope from which the filaments are formed, the amount of the agent $3- 20 so employed depending upon a number of factors, (I) (I) such as the particular cellulose derivative used in making the yarn 'the solvent or solvent com- CH CH CH CH (Ac etonyl acet r i e ditetrahydrofurfuryl dimethylene ketal) blnatlon used In making p the Splnnnlg sulution, 65 g fgfi gfiggg g' n 28 and the degree of softness or pliability desired in white mineral mi 10 the yarn, etc. g gg f fi g g If the conditioning agent is to be applied to ivater.. IIIII 7 the yarn after spinning, this may be done by 7 l Example 3 br nging the yarn in contact with a wick, roll, or

felt wet therewith, or the liquid may be applied CHPC CHFCHPCO, by immersion, spray, or otherwise. The particu- 9: 4 lar point at which the liquid is applied may vary. 2223? 'ethoxy'B'ethoxy ethyl It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the 76 guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. In some cases, the liquid may even be applied to the yarn after winding onto cones,

spools, bobbins, or. the like or by the so-called bobbin to bobbin method. In the or e of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific nature of the material to which the agent is applied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 4 to or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples l have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such'as solvents, non-solvents, emulsifying agents, blending agents and the like, may be added within the scope of my invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or fugitively tint or dye the material undergoing treatment.

Although I have found it convenient toillustrate my. invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired tocontrol the solvent or softening action of the conditioning agent, the amount of the agent may be adjusted as, for example, by reducing the amount of the agent and correspondingly increasing the amount of oil or other ingredient.

While I have described my invention with particular reference to the treatment of yarns composed of organic derivatives of cellulose such as cellulose acetate, the conditioning agents and formulas described herein are applicable to the conditioning of many other types of cellulose derivative yarns such as those composed of or containing cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

The term yarn as used herein and in the claims is to be understood as including a single filament, a plurality of filaments associated into the form of a thread, either of high or low twist, single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a composite thread formed by twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditioning agents of my invention are exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, castor, neatsfoot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and compositions of my invention possess many outstanding advantages. The fundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed of or containing organic derivatives of cellulose such as cellulose acetate and render them soft and pliable and amenable to various textile operations, especially operations such as those involved in weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and methods of my invention as herein described, one is enabled to obtain highly satisfactory results in themanufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch:-

distortion, laddering and the like.

Use or COMPOUNDS As PLASTICIZERS Example 13 Parts Cellulose acetate 100 CH3CC2H4C O-GH:

O O 80 C H2-C C H? 0 H (Monoglycerol acetonyl acetone) Acetone 400 Example 14 Cellulose acetate 100 CHx-C-CnHl-C O-CH;

o o 20 CHzCH-CH2O8-C2Hs (Monoglycerol acetonyl acetone proplonate) Acetone 300 Methanol 100.

Example 15 Cellulose acetate 100 C s7CC2H4--/C CH:

0 O 0 O CH2 CH-CHgOH CH CHOHOH (Di glycerol acetonyl acetone) Ethylene chloride 400 Dioxane 100 Example 16 Cellulose acetate 100 CHa-C-C H2 om-o-om O O O O CH:CH-CHi-O8CH: CH:-CHCII2O8CH| 20 (Diglycerol acetonyl acetone diacetate) 3733-- Hz CH CHg (Acetonyl acetone ditetrahydroiurluryl dimethyleue ketal) Propylene chloride 300 mfnm: Y 100 Example 20 Cellulose acetate butyratenu 100 CHr-(f-CHr-CHrC OCHs 03134-0 Calla-O CzHs)? (Mono di-Bethoxy-fl-ethoxyethyl keta1)- Triphenyl phosph 8 Ethylene chloride 400 Methanol 100 Compositions of matter prepared as abovedescribed may be deposited upon any suitable filmforming surface to form a film or sheet, as is well known to those skilled in the art. A film so produced has permanently brilliant transparency and low inflammability, burning no more readily than ordinary newsprint. Such film is exceedingly tough and flexible, as shown by the fact that it will withstand many folds upon a modified Schopper'fold-tester (commonly used for such purposes) without breaking and that even after being subjected for a considerable number of days to air maintained at a temperature of 65 C. the film still maintains flexibility (in contrast to almost complete'lack of flexibility where no plasticizer is used) demonstrating that the.

film will withstand ordinary usage satisfactorily for many years. The sum total of the above advantageous properties of a product produced from my new composition is considerably in excess of that of products produced-with what have previously been regarded as the better plasticizers.

In order that those skilled in this art may better understand my invention I would state, by way of illustration, that for themanufacture of photographic film or other sheets my new composition of matter may in general becompounded as follows: 100 parts of acetone soluble cellulose acetate, i.'e., cellulose acetate contain-- ing from 38% to 42% lacetylradical, approximately, is dissolved with stirring at atmospheric temperature in 300 to 500 parts preferably 400 parts, by weight, of acetoneofTo-lthis solution may be added from -50 parts by weight, of any one of the above plasticizers, it being found preferable to employ approximately 30 to 40 parts thereof: The amount of plasticizer may be decreased or' increased, depending upon whether it is desired to decrease or increase, respectively the properties which this plasticizer contributes to the finished product. The amount of solvent employed may also be decreased or increased, depending upon whether it is desired to have a more or less freely flowing composition, respectively.

Other similar solvents than those mentioned above which are compatible with the cellulose acetate and my new plasticizers may also occur I to those skilled in this art. In like manner my plasticizers may be compounded with other single or mixed organic esters of cellulose, such as cellulose aceto-stearate, aceto-malate; or cellulose nitro-acetate, or with the cellulose others, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

My novel plasticizers may be employed also with advantage in connection with a number of the known lacquer and varnish formulas with which it may be found to be compatible. In such cases the plasticizer is usually first put into solution with the cellulose derivative solution and, if non-solvents are added, only to such an extent as will not precipitate the derivative from solution. Also the plasticizer is usually employed in larger amounts, such as from 50 to 60 parts, in compounding lacquers. scope of my invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto.

What I claim is:

Other uses within the 1. The process of conditioning yarn composed of or containing organic derivatives of cellulose to render it amenable to textile operations, including knitting, weaving, and spinning, which comprises applying to the yarn a lubricating composition containing as its essential lubricating component an acetal selected from the group consisting of the mono and di-ketals of acetonyl acetone derived from glycols, alkoxy alcohols and tetrahydrofurfuryl alcohol.

2. The process of conditioning yarn composed of or'containing cellulose acetate to render it amenable to textile operations, including knitting, weaving, and spinning, which comprises applying to theyarn a lubricating composition containing as its essential lubricating component an acetal selected fromthe groupconsisting of the monoand di-ketals of acetonyl acetone derived from glycols, alkoxy alcohols and drofurfuryl alcohol.

3. Textile yarns composed of or containing organic derivatiyes of cellulose, amenable to textile operations, including knitting, weaving, and spinning, said yarns being impregnated with a lubricating agent comprising an acetal selected from the group consisting of the mono and di-ketals tetahyof 'acetonylacetone derived from glycols, alkoxy comprising an acetal selected from the group consisting of the. mono and di-ketals of acetonyl.

acetonederived from glycols, alkoxy alcohols and tetrahydrofurfuryl. alcohol.

JOSEPH mcxmi'. 

